Morphology,thermal, and mechanical properties of polyamide 66/clay nanocomposites with epoxy‐modified organoclay

A new kind of organophilic clay, cotreated by methyl tallow bis‐2‐hydroxyethyl quaternary ammonium and epoxy resin into sodium montmorillonite (to form a strong interaction with polyamide 66 matrix), was prepared and used in preparing PA66/clay nanocomposites (PA66CN) via melt‐compounding method. Three different types of organic clays, CL30B–E00, CL30B–E12, and CL30B–E23, were used to study the effect of epoxy resin in PA66CN. The morphological, mechanical, and thermal properties have been studied using X‐ray diffraction, transmission electron microscopy (TEM), mechanical, and thermal analysis, respectively. TEM analysis of the nanocomposites shows that most of the silicate layers were exfoliated to individual layers and to some thin stacks containing a few layers. PA66CX–E00 and PA66CX–E12 had nearly exfoliated structures in agreement with the SAXS results, while PA66CX–E23 shows a coexistence of intercalated and exfoliated structures. The storage modulus of PA66 nanocomposites was higher than that of the neat PA66 in the whole range of tested temperature. On the other hand, the magnitude of the loss tangent peak in α‐ or β‐transition region decreased gradually with the increase in the clay loading. Multiple melting behavior in PA66 was also observed. Thermal stability more or less decreased with an increasing inorganic content. Young's modulus and tensile strength were enhanced by introducing organoclay. Among the three types of nanocomposites prepared, PA66CX–E12 showed the highest improvement in properties, while PA66CX–E23 showed properties inferior to that of PA66CX–E00 without epoxy resin. In conclusion, an optimum amount of epoxy resin is required to form the strong interaction with the amide group of PA66. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1711–1722, 2006     

Anionic Clays as Potential Slow-Release Fertilizers: Nitrate Ion Exchange

Several nitrate containing anionic clays were synthesized at different temperatures and the kinetics of NO₃ ^– release were determined to test their suitability as slow-release N fertilizers. A sample (Mg:Al = 2:1) synthesized at 60°C with smaller particle size released 75, 86 and 100% of its NO₃ ^– in 1, 3 and 7 days, respectively when equilibrated with a simulated soil solution. On the other hand, the 175°C/2 hrs sample with larger particle size released 65, 77 and 84% of its nitrate in 1, 3 and 7 days, respectively. Another anionic clay (synthesized at 175°C/24 hrs) of higher charge density (Mg:Al = 2:1) containing NO₃ ^– was equilibrated with a 0.012 N NaCl or Na₂CO₃ to test the role of different anions in releasing the NO₃ ^– anion from the interlayers. The results showed that Cl^– released more NO₃ ^– than did CO₃ ^2– from this anionic clay after all the treatment times probably as a result of the CO₃ ^2– anion blocking the release of NO₃ ^– from the interior of the crystals. When a lower charge density (Mg:Al = 3:1) sample (synthesized at 175°C/48 hrs) was equilibrated with 0.02N solution of anions the release of nitrate was as follows: Cl^– < F^– < SO₄ ⁼ CO₃ ^2–. These results suggest that the divalent SO₄ ⁼ and CO₃ ^2– anions are more effective in the release of NO₃ ^– from this lower charge density anionic clay. Time-resolved structural analysis of NO₃ ^– exchange with CO₃ ^2– in the above anionic clay using synchrotron x-ray diffraction showed that ion exchange is rapid because of small crystal size and lower charge density. Thus the release of NO₃ ^– from anionic clays is an interplay among the type of anions present in soil solution, their concentration, pH of soil solution, the charge density and crystal size of anionic clay etc.     

Melt‐compounded natural rubber nanocomposites with pristine and organophilic layered silicates of natural and synthetic origin

Composites based on natural rubber (NR) and containing organophilic and pristine layered silicates of natural and synthetic origin were produced by melt compounding and sulfur curing. The curing, thermomechanical, and mechanical properties of the mixes, which contained 10 phr (parts per hundred parts of rubber) silicates, were determined. The dispersion of the silicates was studied by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Organophilic clays accelerated the sulfur curing of NR, which was believed to occur because of a complexation reaction in which the amine groups of the clay intercalants participated. The property improvements caused by the fillers were ranked as follows: organophilic clays > pristine synthetic layered silicate (sodium fluorohectorite) > pristine natural clay (purified sodium bentonite) > precipitated nonlayered silica (used as a reference). This was attributed to partial intercalation of the organophilic clay by NR on the basis of XRD and TEM results and to the high aspect ratio of the fluorohectorite. Apart from intercalation, severe confinement (i.e., the collapse of the interlayer distance) of the organoclays was observed. This peculiar feature was traced to the formation of a zinc coordination complex, which extracted the amine intercalant of the organoclays, thus causing the collapse of the layers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 813–819, 2004     

活化高岭土适宜煅烧温度

影响高岭土适宜煅烧温度的因素包括煅烧时间、升温速度、煅烧气氛、炉窑、煅烧方式,生料颗粒堆集状态等,但最不可控的因素是高岭土本身的性质。任一“最佳煅烧温度”都是针对某一具体情况的。选择高岭土适宜煅烧温度既要考虑技术因素．又须兼顾经济效果。对于某种性质未知的高岭土,最简单的选择其适宜煅烧温度的方法是通过DTA／TGA来进行。     

Polar and Non-Polar Solvent Permeation Resistance of Blow-Molded Bottles of Polyethylene/Blends of Modified Polyamide and Polyamide 6 Clay Nanocomposite

Investigations on white spirit and acetone permeation resistance of modified polyamide and nylon 6 clay (MPANYC) blends and their corresponding polyethylene/MPANYC bottles were reported in this study. The white spirit and acetone permeation resistance of MPANYC sheets improve consistently with increasing NYC contents present in MPANYC resins after blending nylon 6 clay (NYC) in modified polyamide (MPA) resins. However, the order of barrier improvement of the PE/MPANYC and PE/NYC bottle specimens is not corresponding to the order of barrier improvement of the MPANYC and/or NYC barrier resins added in PE. The blow-molded PE/NYC bottle specimen exhibits similarly worse white spirit and acetone solvent permeation resistance as the PE bottle specimen, wherein no clearly formed NYC laminas but only dispersed NYC droplets or agglomerates were found on the fracture surfaces of the PE/NYC bottles. However, after blending optimum compositions of MPANYC in PE, the PE/MPANYC bottles with demarcated MPANYC laminas exhibit significantly better white spirit and acetone permeation resistance than the PE/MPA bottle, wherein the white spirit and acetone permeation rates of the PE/MPA₈NYC₁ bottle are about 1.3 and 1.4 times slower than those of the PE/MPA bottle, respectively. In order to understand these interesting barrier properties of PE/MPANYC and PE/NYC bottles, rheological, thermal, wide angle X-ray diffraction and morphological properties of the base MPANYC and NYC resins and their corresponding morphology present in the blow-molded bottles were investigated.     

循环荷载作用下重塑饱和粉黏土的刚度弱化特性研究

以东海大桥海上风电场项目为课题背景,通过动三轴系统对重塑饱和粉质黏土开展一系列长期不排水循环加载三轴试验,分别考虑围压、动应力比和频率3种因素,特别是对高频(f5 Hz)下土体的动力弱化特性进行了研究。试验结果表明:累积塑性应变与累积孔压随着循环次数的增加而增大并且趋于稳定,呈现出应变软化和孔压软化现象。割线动变形刚度模量和割线动弹性刚度模量则随着循环次数的增加,先急剧降低然后趋于稳定,从而表现出刚度弱化现象。进一步研究了割线动弹性刚度模量与循环应变幅值的关系,割线动弹性刚度模量的衰减趋势受动应力比和频率的影响不大,与围压有关,围压越大,割线动弹性刚度模量衰减趋势越慢,衰减稳定幅值越低。     

以废白土制备洗涤膏

植物油脱色用过的活性白土是含油的废白土 ,本文探索了一种充分利用废白土的方法。以强碱与废白土含的油按化学计量比进行皂化反应可得一种洗涤膏。这种洗涤膏主要适用机械工人洗手 ,也可用以清洗瓷砖等硬表面。通过对比试验 ,表明该洗涤膏在这两类应用场合中的洗涤效果良好     

Rubber–clay nanocomposite by solution blending

Ethylene vinyl acetate rubber (45% vinyl acetate content, EVA‐45) and organomodified clay (12Me‐MMT) composites were prepared by solution blending of the rubber and the clay. A combination of X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy studies showed that the composites obtained are on the nanometer scale. The measurements of the dynamic mechanical properties for different compositions over a temperature range (?100 to +100°C) showed that the storage moduli of these rubber–clay nanocomposites are higher above the glass to rubber transition temperature compared to the neat rubber. The tensile strength of the nanocomposites is about 1.6 times higher than that of the EVA‐45. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2216–2220, 2003     

Time and shear dependent rheology of maleated polyethylene and its nanocomposites

Dipole-dipole and/or hydrogen-bonding interactions between the pendant functional groups within maleated high-density polyethylene (PE-g-MAn) establish a physical polymer network, whose formation kinetics and shear-sensitivity are revealed by dynamic oscillatory testing. The pronounced time and shear dependent viscoelastic properties of PE-g-MAn were not observed for a corresponding imide derivative, PE-g-imide, presumably due to weakened functional group associations in the latter material.The melt compounding of PE-g-MAn with onium-ion exchanged montmorillonite clay (NR₄⁺-MM) resulted in a partially exfoliated hybrid nanocomposite structure, whose viscoelastic behaviour differed significantly from that of the unfilled polymer. The presence of dispersed clay platelets altered the extent of functional group associations, thereby changing the dynamics of network formation.     

The linear viscoelastic properties of copolypropylene–clay nanocomposites

The linear viscoelastic properties of copolypropylene (cPP)–clay nanocomposites (cPPCNs) prepared by melt intercalating with different amounts of clay were extensively examined by rheological measurements. Meanwhile, the clay effects on the cPP confinements were first estimated by calculating the activation energy of different cPP moving units, including the whole molecular chain, the chain segment, and smaller unit such as chain link. The results showed that the stability of cPPCNs melts wrecked when the clay loading was above 5 wt %. An increase in clay loading of cPPCNs gave rise to a strong low frequency solid‐like response (G′ > G″). Unlike the matrix polymer, cPPCN5 (with 5 wt % clay) exhibited a relaxation plateau as relaxation time prolonged above 100 s, and displayed a maximal linear modulus. The variations of the activation energy of different cPP moving units revealed that the mobility of cPP molecular chains was restricted by clay layers, while these restrictions were not only related to the clay loadings but also largely depended on the clay dispersion status in the matrix. The motions of cPP chain segments were greatly limited at 3–5 wt % loading of clay, but drastically activated with the addition of 7 wt % clay due to the increasing stacks of clay layers within the matrix. However, it was found that the presence of clay had little effect on the mobility of small cPP moving units such as chain links. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1523–1529, 2006